WO2007108426A1 - Batterie électrolytique non aqueuse et son procédé de fabrication - Google Patents

Batterie électrolytique non aqueuse et son procédé de fabrication Download PDF

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Publication number
WO2007108426A1
WO2007108426A1 PCT/JP2007/055446 JP2007055446W WO2007108426A1 WO 2007108426 A1 WO2007108426 A1 WO 2007108426A1 JP 2007055446 W JP2007055446 W JP 2007055446W WO 2007108426 A1 WO2007108426 A1 WO 2007108426A1
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Prior art keywords
separator
electrolyte battery
positive electrode
battery
nonaqueous electrolyte
Prior art date
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PCT/JP2007/055446
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English (en)
Japanese (ja)
Inventor
Hiroshi Minami
Takeshi Ogasawara
Naoki Imachi
Atsushi Kaiduka
Yasunori Baba
Yoshinori Kida
Shin Fujitani
Original Assignee
Sanyo Electric Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006171450A external-priority patent/JP4958484B2/ja
Priority claimed from JP2006207450A external-priority patent/JP5110817B2/ja
Priority claimed from JP2006207451A external-priority patent/JP5110818B2/ja
Application filed by Sanyo Electric Co., Ltd. filed Critical Sanyo Electric Co., Ltd.
Priority to US12/293,399 priority Critical patent/US20090136848A1/en
Priority to CN2007800177546A priority patent/CN101443948B/zh
Publication of WO2007108426A1 publication Critical patent/WO2007108426A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • Non-aqueous electrolyte battery and manufacturing method thereof are non-aqueous electrolyte battery and manufacturing method thereof.
  • the present invention relates to a nonaqueous electrolyte battery such as a lithium ion battery or a polymer battery, and an improvement of the manufacturing method thereof, and particularly has high reliability even in a battery configuration characterized by excellent cycle characteristics and storage characteristics at high temperatures and high capacity. This is related to the battery structure etc. that can demonstrate its properties.
  • Lithium ion batteries that charge and discharge when lithium ions move between the positive and negative electrodes along with charge and discharge have high energy density and high capacity. Therefore, they are used as the driving power source for such mobile information terminals. Widely used.
  • the mobile information terminal has a tendency to further increase the power consumption as the video playback function, the game function, and! / Are enhanced, and the lithium ion battery that is the driving power source is long. For the purpose of time reproduction and output improvement, there is a strong demand for higher capacity.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-141042
  • lithium cobaltate is used as the positive electrode active material and graphite is used as the negative electrode active material.
  • the remaining capacity after storage decreases significantly, and sometimes decreases to almost zero. Therefore, when this battery was disassembled, a large amount of coroline was detected from the negative electrode and the separator, and therefore, the degradation mode was thought to be accelerated by the positive power and the eluting coroline element.
  • a layered positive electrode active material, such as lithium cobaltate increases in valence due to extraction of lithium ions. Since tetravalent condensate is unstable, the crystal itself is not stable and the structure is stable.
  • the present invention provides a nonaqueous electrolyte battery that is excellent in cycle characteristics and storage characteristics at high temperatures and that can exhibit high reliability even in a battery configuration characterized by high capacity, and a method for manufacturing the same. For the purpose of providing!
  • the present invention relates to an electrode body comprising a positive electrode having a positive electrode active material layer containing a positive electrode active material, a negative electrode having a negative electrode active material, and a separator interposed between the two electrodes.
  • the positive electrode active material contains at least cobalt or manganese
  • the separator includes a porous separator body and And a coating layer formed on at least one surface of the separator body, and the coating layer is composed of a filler particle and a water-insoluble binder.
  • the water-insoluble binder contained in the coating layer disposed on the surface of the separator main body absorbs the electrolyte solution and swells, so that the filler water particles are moderately spaced by the swollen water-insoluble binder.
  • a coating layer filled with filler particles and a water-insoluble binder exhibits an appropriate filter function. Therefore, the decomposition product of the electrolyte reacted at the positive electrode and the cobalt ions and manganese ions eluted from the positive electrode active material force are trapped by the coating layer, thereby suppressing the precipitation of manganese on the separator and Z or the negative electrode. it can.
  • the separator body force can also be prevented from falling off the coating layer, and the above effects can be achieved over a long period of time. Sustained.
  • a water-insoluble binder is used, the dispersibility of the filler particles can be ensured only by mixing the water-insoluble binder, the filler particles, and the organic solvent, so that the coating layer can be easily produced. it can.
  • the concentration of the water-insoluble binder with respect to the filler particles is preferable to regulate the concentration of the water-insoluble binder with respect to the filler particles to 50% by mass or less, desirably 10% by mass or less, and more desirably 5% by mass or less. It is preferable to regulate in this way when the concentration of the water-insoluble binder becomes too high.
  • the water-insoluble binder comprises a copolymer containing acrylonitrile units and Z or a polyacrylic acid derivative.
  • the copolymer containing the acrylonitrile unit can fill the gaps between the filler particles by swelling after absorbing the electrolyte, and has a strong binding force with the filler particles. It is possible to prevent the filler particles from re-aggregating by sufficiently securing the dispersibility of the filler, and to have a characteristic that the elution into the non-aqueous electrolyte is small. This is because.
  • the coating layer is desirably formed on the surface of the separator body on the positive electrode side.
  • the coating layer is formed on the surface of the separator body on the positive electrode side, the decomposition product of the electrolytic solution reacted at the positive electrode, the positive electrode active material force, the eluting cobalt ion and manganese ion force immediately (before moving to the separator) This is because the above effect can be further exhibited.
  • the coating layer contains a water-soluble binder, and the coating layer is formed on the surface of the separator body on the negative electrode side.
  • a separator In a non-aqueous electrolyte battery, it is essential for ensuring safety that a separator has a current interruption mechanism (so-called shutdown mechanism) due to microporous blockage. ) Melting point. Therefore, when the covering layer is formed, the function may be impaired if the separator is heated to a predetermined temperature or higher.
  • a binder (binder) for forming the coating layer it is also possible to use only a water-insoluble binder such as PVDF or acrylic polymer as described above.
  • NMP N-methylpyrrolidone having a boiling point of 200 ° C. or more is often used as a result.
  • the water-insoluble binder comprises a non-fluorine-containing polymer, and the water-soluble binder is a cellulosic polymer or an ammonium salt, an alkali metal salt, a polyacrylic acid ammonium salt, a polycarboxylic acid ammonia.
  • -Um salt power group power It is preferable that at least one power selected is also configured.
  • the coating layer preferably contains a surfactant.
  • polyethylene is used as a separator, and this polyethylene repels water. Therefore, it is desirable to add a surfactant that exerts a surface active action to the coating layer.
  • a separator that does not repel water is used, or a separator that exhibits a surface active action is used, it is not necessary to add a surfactant.
  • the ratio of the water-insoluble binder to the total amount of the solid content is 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less.
  • solid content means a filler particle, a water-insoluble binder, and a water-soluble binder, and when a surfactant is contained, it contains a surfactant.
  • the total amount of solids excluding filler particles relative to the amount of filler particles is desirably 30% by mass or less.
  • the thickness of the separator body is X ( ⁇ m) and the porosity of the separator body is y (%), the value obtained by multiplying X and y is 1500 (m '%) or less. It is desirable to be regulated so that
  • the reason for this restriction is that the smaller the pore volume of the separator body, the more affected by the precipitates and side reactants, and the quicker the characteristic deterioration becomes. Therefore, the battery having the separator body thus restricted is used. This is because by applying the present invention, a remarkable effect can be exhibited.
  • the separator can be thinned, so that the energy density of the battery can be improved.
  • the filler particles are composed of inorganic particles, in particular, rutile-type titers and Z or alumina.
  • the filler particles are limited to inorganic particles, particularly rutile-type titers and Z or alumina. These are excellent in stability in the battery (low reactivity with lithium). This is because the cost is low.
  • the rutile structure is used because the anatase structure can insert and release lithium ions, and depending on the environmental atmosphere and potential, it absorbs lithium and develops electron conductivity. It is also a power that has a risk of capacity reduction and short circuit.
  • the average particle size of the filler particles be regulated so as to be larger than the average pore size of the separator body.
  • the filler particles preferably have an average particle size of 1 ⁇ m or less.
  • those having a surface treatment with aluminum, silicon and titanium are preferred.
  • the coating layer preferably has a thickness of 4 m or less, particularly 2 m or less.
  • the thickness force of the coating layer is m or less, particularly 2 m or less.
  • the thickness of the coating layer means the thickness when the coating layer is formed on one side of the separator, and the thickness on one side when the coating layer is formed on both sides of the separator. It shall be said.
  • the packing density of the positive electrode active material layer is preferably 3.40 gZcc or more.
  • the packing density is less than 3.40 gZcc
  • the reaction at the positive electrode reacts as a whole rather than a local reaction, so the deterioration at the positive electrode proceeds uniformly and is preserved. There is no significant effect on the subsequent charge / discharge reaction.
  • the packing density is 3.40 gZcc or more
  • the reaction at the positive electrode is limited to the local reaction at the outermost surface layer, so that the deterioration at the positive electrode is also deteriorated at the outermost surface layer. Become the center. For this reason, the penetration and diffusion of lithium ions into the positive electrode active material during discharge become rate-limiting, and the degree of deterioration increases. For this reason, when the packing density of the positive electrode active material layer is 3.40 gZcc or more, the effects of the present invention are sufficiently exhibited.
  • the positive electrode be charged until it becomes 4.30 V or higher, preferably 4.40 V or higher, particularly preferably 4.45 V or higher with respect to the lithium reference electrode potential.
  • the positive electrode is charged at less than 4.30 V with respect to the lithium reference electrode potential, there is not much difference in high-temperature characteristics depending on the presence or absence of the coating layer, but the positive electrode 4.
  • the positive electrode is particularly noticeable in batteries where the positive electrode is charged at 4.40V or higher, or 4.45V or higher relative to the lithium reference electrode potential.
  • the positive electrode active material contains at least lithium cobaltate in which aluminum or magnesium is dissolved, and the lithium cobaltate surface is in electrical contact with lithium cobaltate. It is desirable that the zircouore is fixed.
  • the reason for such a structure is as follows. That is, when lithium cobaltate is used as the positive electrode active material, the crystal structure becomes unstable as the charging depth increases, and the deterioration is accelerated in a high temperature atmosphere. Therefore, aluminum or magnesium is dissolved in the positive electrode active material (inside the crystal) to reduce crystal distortion at the positive electrode.
  • these elements greatly contribute to the stability of the crystal structure, This leads to a decrease in the initial charge / discharge efficiency and a decrease in the discharge operating voltage. Therefore, zinc cores in electrical contact with lithium conoleate are fixed on the surface of the lithium cobaltate to alleviate such problems.
  • the present invention provides an electrode body comprising a positive electrode having a positive electrode active material layer containing a positive electrode active material, a negative electrode, and a separator interposed between the two electrodes, a solvent, and lithium And a non-aqueous electrolyte battery in which the non-aqueous electrolyte is impregnated in the electrode body, wherein the positive electrode active material contains at least cobalt or manganese, and the surface of the separator on the positive electrode side And Z or a coating layer containing inorganic particles and a binder is formed on the surface of the negative electrode side of the separator, and the lithium salt contains LiBF. .
  • the positive electrode is charged until it becomes 40 V or higher.
  • the LiBF-derived film is the positive electrode active material.
  • the reason why the coating layer exhibits the filter function is that the binder contained in the coating layer absorbs the electrolytic solution and swells, so that the inorganic particles are appropriately filled with the swelled binder. It is considered a thing. Further, a complicated filter layer is formed by forming a layer in which a plurality of inorganic particles are entangled, and it is considered that the physical trapping effect is enhanced.
  • the positive electrode is charged to 4.40V or higher with respect to the lithium reference electrode potential for the following reason. That is, LiBF as described above is on the positive electrode surface.
  • LiBF is highly reactive with the positive electrode.
  • the charge curve will meander and the amount of charge will increase greatly when the battery is recharged after storage.
  • the configuration of the present invention can eliminate the occurrence of such abnormal charging behavior, it is confirmed that there is an effect.
  • the effect of the present invention can be achieved by simply adding LiBF to the electrolyte.
  • the coating layer is formed on the entire surface of the positive electrode side of the separator and the entire surface of Z or the negative electrode side of the separator.
  • the ratio of the LiBF to the total amount of the nonaqueous electrolyte is 0.1 mass% or more and 5.0 mass%.
  • the ratio of LiBF to the total amount of non-aqueous electrolyte is 0.1 mass.
  • the lithium salt contains LiPF, and the concentration of LiPF is 0.6 mol.
  • LiBF reacts and is consumed by charging and discharging, so when the electrolyte is LiBF alone
  • the lithium salt contains LiPF. Also, LiPF is included in the lithium salt
  • the concentration of 6 is preferably 0.6 mol Z liter or more.
  • the concentration of 6 is less than 2.0 mol Z liters.
  • the inorganic particles are composed of rutile-type titer and Z or alumina.
  • inorganic particles such as zirconia and magnesia may be used as described above.
  • the average particle size of the inorganic particles is preferably 1 ⁇ m or less, and considering the dispersibility of the slurry, it is preferable that the surface treatment is performed with aluminum, silicon, or titanium. It is. [0049] It is desirable that the thickness of the coating layer be 4 ⁇ m or less.
  • the thickness of the coating layer is particularly preferably 2 m or less.
  • the coating layer is intricately complicated, the trapping effect is sufficiently exhibited even when the thickness is small.
  • LiBF is added to the electrolyte.
  • the thickness of the coating layer should be 1 ⁇ m or more.
  • the thickness of the coating layer is preferably 1 ⁇ m or more and 4 m or less, and particularly preferably 1 ⁇ m or more and 2 / zm or less.
  • the thickness of the said coating layer shall mean the thickness in one side.
  • the binder concentration with respect to the inorganic particles is regulated to 50% by mass or less.
  • the upper limit is determined in this way for the same reason as described above. Further, considering this reason, it is further desirable that the binder concentration relative to the inorganic particles is 10% by mass or less, and among these, it is particularly desirable to be 5% by mass or less.
  • the packing density of the positive electrode active material layer is preferably 3.40 gZcc or more.
  • the positive electrode be charged until it becomes 4.45V or more, preferably 4.50V or more with respect to the lithium reference electrode potential.
  • the positive electrode active material is a cover in which at least aluminum or magnesium is dissolved. Desirably, lithium tortate is contained, and zircoure is fixed to the surface of the lithium cobaltate.
  • the thickness of the separator is X ( ⁇ m) and the porosity of the separator is y (%), the value obtained by multiplying X and y is 800 ⁇ ⁇ %) or less. It is preferably applied to regulated batteries.
  • the reason for restricting the pore volume of the separator to 800 (m '%) or less is for the same reason as described above.
  • the separator has a small pore volume and the battery can be made thinner, the energy density of the battery can be improved.
  • the present invention applies a slurry containing filler particles, a water-insoluble binder and an organic solvent to at least one surface of a porous separator body, and dries the slurry.
  • the separator is disposed between a step of forming a separator by forming a coating layer on the surface, a positive electrode having a positive electrode active material containing at least cobalt or manganese and lithium, and a negative electrode having a negative electrode active material. And a step of impregnating the electrode body with a nonaqueous electrolyte as a binder for forming a separator coating layer by such a manufacturing method.
  • a non-aqueous electrolyte battery using only a non-water-soluble binder can be produced.
  • the dip coating method As a coating method, the dip coating method, gravure coating method, die coating method, transfer method, etc. can be considered. With the exception of the dip coating method, slurry must be applied to each side of the separator body. However, since the separator body is a microporous membrane, when the slurry is applied to one surface, the slurry penetrates to the other surface side, resulting in diluting water-insoluble binder concentration in the coating layer. As a result, the action and effect of the water-insoluble binder in the coating layer may not be sufficiently exerted, and the force may be increased. In addition, an increase in the concentration of the water-insoluble binder in the separator body may cause inconveniences such as deterioration of the air permeability of the separator body. Therefore, in order to avoid such inconvenience, it is desirable to adopt the above dip coating method.
  • both sides can be applied at one time, so that the manufacturing cost can be reduced, and a uniform coating layer can be formed on both sides by changing the slurry concentration and coating speed. And the advantage is also demonstrated.
  • the present invention applies a slurry containing filler particles, a water-insoluble binder, a water-soluble binder, and water to one surface of a porous separator body, and then dried. Then, by forming a coating layer on one surface of the separator body, a step of producing a separator, a positive electrode having a positive electrode active material containing at least conoretate or manganese and lithium, and a negative electrode having a negative electrode active material A step of producing an electrode body by placing a separator between both electrodes in a state where the coating layer is disposed on the negative electrode side, and impregnating the electrode body with a nonaqueous electrolyte. According to such a production method, a non-aqueous binder using a water-insoluble binder and a water-soluble binder as a binder when forming the coating layer of the separator. An electrolyte battery can be manufactured.
  • the slurry preferably further contains a surfactant.
  • the separator In the step of manufacturing the separator, it is desirable to use a doctor blade method, a gravure coating method, a transfer method or a die coating method as a method for forming the coating layer. This is because the dip coating method requires both coatings on the separator, but the doctor blade method can facilitate one-sided coating of the separator.
  • the coating layer disposed on the surface of the separator main body exhibits an appropriate filter function, cobalt ions and manganese ions eluted from the decomposition product of the electrolytic solution reacted at the positive electrode and the positive electrode active material Can be prevented from being trapped by the coating layer and precipitating cobalt or manganese by the separator.
  • damage to the negative electrode separator is reduced, so that an excellent effect is obtained in that deterioration of cycle characteristics at high temperatures and deterioration of storage characteristics at high temperatures can be suppressed.
  • a LiBF-derived film is formed by adding LiBF to the electrolytic solution.
  • the coating layer arranged between the positive electrode and the separator exerts an appropriate filter function, the decomposition products and cobalt ions are trapped in the coating layer, and cobalt and manganese are mixed in the negative separator. Precipitation can be sufficiently suppressed. As a result, damage to the negative electrode separator is drastically reduced, so that it is possible to suppress deterioration of cycle characteristics at high temperatures and storage characteristics at high temperatures.
  • the inorganic particles and the coating layer and the positive electrode active material layer or the separator are firmly bonded to each other by the binder, it is possible to suppress the coating layer from falling off the positive electrode active material layer or the separator cover. There is also an effect.
  • lithium cobalt oxide Al and Mg are each dissolved in 1. Omol% and Zr is present on the surface of 0. O5mol%) as a positive electrode active material, and acetylene as a carbon conductive agent.
  • Black and PVDF as a binder were mixed at a mass ratio of 95: 2.5: 2.5, and then stirred using a special machine combination with NMP as a solvent.
  • a slurry was prepared.
  • this positive electrode mixture slurry was applied to both surfaces of an aluminum foil as a positive electrode current collector, and further dried and rolled to produce a positive electrode in which a positive electrode active material layer was formed on both surfaces of the aluminum foil. did.
  • the packing density of the positive electrode active material layer was 3.60 gZcc.
  • a negative electrode slurry by mixing carbon material (artificial graphite), CMC (carboxymethyl cellulose sodium), and SBR (styrene butadiene rubber) in an aqueous solution at a mass ratio of 98: 1: 1, A negative electrode slurry was applied to both surfaces of a copper foil as a current collector, and further dried and rolled to produce a negative electrode.
  • the packing density of the negative electrode active material layer was 1.60 gZcc.
  • LiPF is mainly dissolved at a ratio of 1.0 mol Z liter in a mixed solvent in which ethylene carbonate (EC) and jetyl carbonate (DEC) are mixed at a volume ratio of 3: 7.
  • EC ethylene carbonate
  • DEC jetyl carbonate
  • acetone as a solvent and TiO, which is a filler particle [rutile type, having a particle size of 0.3
  • the separator body made of polyethylene (hereinafter abbreviated as PE) (thickness: 18; ⁇ ⁇ , average pore diameter 0.6 / ⁇ ⁇ , porosity 45%)
  • PE polyethylene
  • the slurry was applied using a dip coating method, and the solvent of the slurry was dried and removed to form coating layers on both sides of the separator body. Note that the thickness of this coating layer is 2 m on both sides, and the thickness of the separator body is 18 m as described above. The film thickness is 20 / zm.
  • a lead terminal is attached to each of the positive and negative electrodes, and a spiral wound electrode is pressed through a separator to produce a flattened electrode body, and then an aluminum laminate film is stored as a battery outer package
  • An electrode body was loaded into the space, and a non-aqueous electrolyte was poured into the space, and then an aluminum laminate film was welded and sealed to produce a battery.
  • the end-of-charge voltage is regulated to 4.4V by adjusting the amount of active material of both positive and negative electrodes, and the positive / negative capacity ratio (negative electrode) at this potential.
  • the design capacity of the pond is 780mAh.
  • a battery was produced in the same manner as in the first embodiment except that the separator was produced as follows and the coating layer of the following separator was disposed on the negative electrode side.
  • the filler particle TiO [rutile type, particle size 0.38 m, Titanium Industry Co., Ltd.
  • KR380 10% by weight, 1% by weight of the copolymer (water-insoluble polymer) containing acrylonitrile structure (unit) as the binder, and CMC (carboxymethylcellulose sodium as the thickener). 1% by weight of a water-soluble polymer), 1% by weight of a polyalkylene type nonionic surfactant and 87% by weight of water as a solvent, and mixed and dispersed using a special machine made by Filmic ⁇ Treatment was performed to prepare a slurry in which TiO was dispersed. Next, Polyech
  • the slurry is formed on one side of the separator body made of a microporous membrane (thickness: 18; ⁇ ⁇ , average pore diameter 0.6 ⁇ ⁇ , porosity 45%) was applied using a doctor blade method, and the solvent of the slurry was dried and removed to form a coating layer on one side of the separator body. Since the thickness of this coating layer is 2 m and the thickness of the separator body is 18 ⁇ m, the total thickness of the separator is 20 ⁇ m. [0071] (Third embodiment)
  • a battery was fabricated in the same manner as in the first embodiment, except that the non-aqueous electrolyte prepared as follows was used, and the following was used as the separator.
  • a PE microporous membrane (film thickness: m, average pore size 0.1 ⁇ m, porosity 38%) was used as the separator body, and the gravure coating method was used only on the positive electrode surface of the separator body.
  • a slurry in which 2 was dispersed was applied, further dried and removed.
  • PVDF manufactured by Kureha Chemical Industry Co., Ltd., KF1100, which is usually used for the positive electrode for lithium ion batteries.
  • PVDF for positive electrode PVDF for positive electrode
  • PVDF for gel polymer electrolyte both PVDF—HFP—PTFE
  • PVDF for gel electrolytes Rubbery polymers containing acrylonitrile units were used.
  • [0075] Distributed processing method A disperser dispersion treatment method (3000 rpm for 30 minutes), a special equipment filmics dispersion treatment method (40 mZmin for 30 seconds), and a bead mill dispersion treatment method (1500 rpm for 1, 0 minutes) were used. For reference, untreated samples were also examined.
  • both PVDFs positive electrode PVDF and gel electrolyte PVDF
  • the rubber properties containing atari mouth-tolyl units It was recognized that precipitation was easier than in the case of polymers, and that there was a tendency! Therefore, it is preferable to use a rubbery polymer containing an acrylonitrile unit as a water-insoluble binder. The reason for this will be described below.
  • a coating layer as dense as possible. In that sense, it is preferable to use filler particles of submicron or less. However, although it depends on the particle size, it is necessary to prevent reaggregation after crushing (dispersing) the particles which are easily agglomerated.
  • Water-insoluble binder (specifically, a water-insoluble polymer that functions as a binder)
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • a copolymer containing an acrylonitrile structure (unit) were used.
  • a disperser dispersion method (3000 rpm for 30 minutes), a special machine Filmics dispersion method (40 mZmin for 30 seconds), and a bead mill dispersion treatment method (1500 rpm for 10 minutes) were used.
  • a disperser dispersion method 3000 rpm for 30 minutes
  • a special machine Filmics dispersion method 40 mZmin for 30 seconds
  • a bead mill dispersion treatment method (1500 rpm for 10 minutes) were used.
  • untreated samples were also examined.
  • CMC sodium carboxymethylcellulose, the addition ratio is 1% by mass with respect to the total amount of the slurry
  • thickener a water-soluble binder
  • polyalkylene a surfactant
  • Type nonionic surfactant Addition rate was used 1% by weight
  • copolymers containing SBR and acrylonitrile structures are superior to PTFE in flexibility after drying, and in particular, a thin film is required to have a high degree of freedom.
  • flexibility and strength of the coating layer after coating are important. In that sense, flexibility such as rubber properties is essential, and from this point, a copolymer containing SBR or acrylonitrile structure is desirable.
  • SBR is known to decompose at the positive electrode potential, and the coating layer is not disposed on the surface in contact with the positive electrode (that is, the coating layer is disposed on the negative electrode side surface of the separator), but electrochemically. It is not preferable to use an unstable material as a water-insoluble binder. For these reasons, a copolymer containing an acrylonitrile structure is most desirable as the water-insoluble binder.
  • the slurry was applied to both sides of the separator body using the dip coating method, gravure coating method, die coating method, doctor blade method, and transfer method.
  • a slurry on one side of the separator body consisting of a microporous membrane must be applied, so when applying slurry on one side, the water-insoluble binder penetrates in the direction of the back side. . For this reason, the concentration of the water-insoluble binder in the coating layer changes (dilutes), or the concentration of the water-insoluble binder in the separator body increases during double-sided coating!] Problems arise. In order to avoid such problems, it is desirable to adopt the dip coating method.
  • the above problem can be suppressed and double-sided coating can be performed at a time, so that the coating process can be simplified, and the force can be applied to both sides by changing the slurry concentration and coating speed.
  • An advantage that a uniform coating layer can be formed can also be exhibited. It should be noted that when force is applied to form a uniform coating layer, it is possible to compress the separator. When compression is performed, there is a high risk of pinholes and the like, which is preferable.
  • the filler particles are adequately filled.
  • the dip coating method can be controlled so that the coating density is low. However, it is preferable to use this method.
  • the solid concentration in the slurry concentration of the filler particles and the water-insoluble binder
  • the slurry Even if the solid content concentration is somewhat high, the coating thickness can be controlled by scraping off or the like. Therefore, the maximum solid content concentration in the slurry is about 60% by mass. be able to.
  • the separator body is often composed of PE (polyethylene) or PP (polypropylene)
  • shrinkage may occur due to the temperature applied during drying.
  • the drying temperature of the slurry is 60 ° C or lower, although it depends on the conditions.
  • the solvent in which the filler particles are dispersed is preferably a highly volatile solvent, and a solvent having a higher volatility and a lower boiling point than NMP generally used in batteries is preferable. Examples of such are acetone and cyclohexane.
  • the concentration of solid components in the slurry (concentration of filler particles, water-insoluble binder, and water-soluble binder) is low due to the necessity of forming a thin film.
  • the coating thickness can be controlled by scraping off. Accordingly, the solid content concentration in the slurry can be up to about 60% by mass.
  • the average particle diameter of the titanium oxide particles in the slurry is 0.38 ⁇ m.
  • a laminate type battery is manufactured using a separator in which a slurry is applied to each separator body to form a coating layer (however, a non-aqueous electrolyte is not injected), and 200V is applied to each battery.
  • a pressure resistance test was also conducted to confirm the presence or absence of a short circuit.
  • the average particle size of the filler particles was larger than the average pore size of the separator body (the average pore size force of the separator body was 0.1 l ⁇ m, 0.3 / zm respectively) ),
  • the filler particles have an average particle size smaller than the average pore size of the separator body, whereas almost no filler particles enter the separator body without blocking the micro-porosity of the separator body as a whole. It was confirmed that the filler particles infiltrated from the surface layer of the separator body to the inside of the separator (with an average pore diameter of 0.6 m).
  • the average particle diameter of the filler particles as a result of the pressure resistance test Is smaller than the average pore size of the separator body, the coating layer is formed, and the defect rate tends to be higher than that of the separator, whereas the average particle size of the filler particles is larger than the average pore size of the separator. The larger one was found to have the same defect rate as the one without the coating layer.
  • the average particle size of the filler particles is preferably larger than the average pore size of the separator body.
  • the average particle size of the filler particles is a value measured by a particle size distribution method.
  • the air permeability of the separator differs depending on the presence or absence of the coating layer, the thickness of the coating layer, etc.
  • the air permeability was measured.
  • an organic solvent was used as the solvent for slurry preparation.
  • a separator made of only PE microporous membrane (separators CS 1 to CS6, changing the average pore diameter, film thickness, and porosity), and PE made A separator with a coating layer formed on the surface of a separator body consisting of a microporous membrane (selected from the above-mentioned separators CS1, CS2, and CS5) (separators IS1 to IS6, with the coating layer thickness changed) Using.
  • This measurement was performed according to JIS P8177, and a B-type Gurley Densometer (manufactured by Toyo Seiki Co., Ltd.) was used as the measuring device.
  • a sample piece is tightened in a circular hole (diameter: 28.6 mm, area: 645 mm 2 ) of the inner cylinder (mass: 567 g), and the air (lOOcc) in the outer cylinder is also transmitted to the outside of the cylinder. The time required for this was measured and this was taken as the air permeability.
  • a separator having a coating layer does not have a coating layer, and has an air permeability compared to the separator. It is recognized that the values have decreased (comparison between separator CS1 and separators IS1 to IS3, comparison between separator CS2 and separator IS4, and separator CS5 Comparison with data IS5). Further, when separators having a coating layer are compared with each other, it is recognized that the air permeability decreases as the thickness of the coating layer increases (separators IS 1 to IS3).
  • a separator having a coating layer using water as a solvent (a separator used in the second embodiment, which has a coating layer using a water-insoluble binder and a water-soluble binder as a binder) And separators used for batteries containing LiBF in the electrolyte
  • the air permeability after the coating layer is formed should be measured.
  • Table 5 and Table 6 show the correspondence between each separator and each battery in order to make it easier to understand whether the separator is used.
  • the air permeability in Tables 5 and 6 is the air permeability in the separator body only (the state in which the coating layer is not formed).
  • Copolymer refers to a copolymer containing an acrylonitrile structure (unit).
  • Separators C S 2 and CS 3 do not have a coating layer and consist only of the separator main body, so the values of the film thickness of the separator main body and the film thickness of the separator are the same.
  • lithium cobalt oxide As described in the background section above, it is preferable to use lithium cobalt oxide as the positive electrode active material in order to increase the battery capacity, but there are also problems. Therefore, various elements were added to lithium cobaltate, which should solve and alleviate the problem, and examined what kind of element is preferable.
  • the addition ratio of Al, Mg, and Zr is not particularly limited.
  • the first to fourth embodiments only the water-insoluble binder is used as the binder (in the case where an organic solvent is used as the solvent, which is the first mode of the best mode for carrying out the invention).
  • the fifth to eighth examples are In the case of corresponding to the second form of the best mode for carrying out), in the ninth and tenth examples, LiBF is added to the nonaqueous electrolyte (
  • Example 1 the battery shown in the first mode in the best mode was used.
  • the battery thus produced is hereinafter referred to as the present invention battery A1.
  • a battery was fabricated in the same manner as in Example 1, except that a separator having an average pore diameter of 0.1 m, a film thickness of 12 ⁇ m, and a porosity of 38% was used. Since the thickness of the coating layer is 2 m on both sides, the total thickness of the separator is 14 ⁇ m.
  • the battery thus produced is hereinafter referred to as the present invention battery A2.
  • a battery was fabricated in the same manner as in Example 1 except that a separator having an average pore diameter of 0.6 m, a film thickness of 23 ⁇ m, and a porosity of 48% was used. Since the thickness of the coating layer is 2 m on both sides, the total thickness of the separator is 25 ⁇ m.
  • the battery thus produced is hereinafter referred to as the present invention battery A3.
  • a battery was produced in the same manner as in Example 1 except that the coating layer was not provided on the separator.
  • the battery thus produced is hereinafter referred to as comparative battery Z1.
  • a battery was fabricated in the same manner as in Comparative Example 1 except that a separator having an average pore diameter of 0.1 m, a film thickness of 12 ⁇ m, and a porosity of 38% was used.
  • comparative battery Z2 The battery thus produced is hereinafter referred to as comparative battery Z2.
  • a battery was fabricated in the same manner as in Comparative Example 1 except that a separator having an average pore diameter of 0.1 m, a film thickness of 16 ⁇ m, and a porosity of 47% was used.
  • comparative battery Z3 The battery thus produced is hereinafter referred to as comparative battery Z3.
  • a battery was fabricated in the same manner as in Comparative Example 1 except that a separator having an average pore diameter of 0.05 ⁇ m, a film thickness of 20 ⁇ m, and a porosity of 38% was used.
  • comparative battery Z4 The battery thus produced is hereinafter referred to as comparative battery Z4.
  • a battery was fabricated in the same manner as in Comparative Example 1 except that a separator having an average pore diameter of 0.6 m, a film thickness of 23 ⁇ m, and a porosity of 48% was used.
  • comparative battery Z5 The battery thus produced is hereinafter referred to as comparative battery Z5.
  • a separator having an average pore diameter of 0.6 / zm, a film thickness of 27 ⁇ m, and a porosity of 52% was used.
  • a battery was fabricated in the same manner as in Comparative Example 1 except for the above.
  • comparative battery Z6 The battery thus produced is hereinafter referred to as comparative battery Z6.
  • Table 7 shows the results of charging and storage characteristics (remaining capacity after storage) of the batteries A1 to A3 and comparative batteries Z1 to Z6 of the present invention.
  • Charge / discharge conditions and storage conditions are as follows.
  • the charging / discharging interval is 10 minutes.
  • the charging / discharging is performed once under the above charging / discharging conditions, and the battery charged to the set voltage by the above charging is left again at 60 ° C for 5 days.
  • the battery is cooled to room temperature, discharged under the same discharge conditions as described above, and the remaining capacity is measured.
  • the remaining capacity was calculated from the equation.
  • the positive electrode active material should be used up to about 4.5V (battery voltage is 0.4V lower than this, 4.4V) based on the lithium reference electrode standard. Considering that
  • the water-insoluble binder in the coating layer is such that it impairs air permeability during separator production. Although there are many that swell more than about 2 times after electrolyte injection, the filler particles in the covering layer are appropriately filled.
  • This coating layer is intricately complicated, and since the particles are firmly bonded to each other by the water-insoluble binder component, the strength is improved and the filter effect is sufficiently exhibited (the thickness is small). Is also an intricate structure, which increases the trapping effect).
  • the determination of the electrolyte absorbency is difficult, but it can be roughly estimated by the time it takes for a drop of PC to disappear.
  • the battery was disassembled and the discoloration of the separator (separator body) and the negative electrode surface was observed.
  • the separator turned brownish after storage.
  • deposits were confirmed on the negative electrode, whereas in the battery of the present invention in which the coating layer was formed, deposits and discoloration on the separator body and the negative electrode surface were not observed, and the coating layer was discolored. It was. From this result, it is presumed that damage to the separator body and the negative electrode is reduced by suppressing the movement of the reaction product at the positive electrode in the coating layer.
  • the power for improving the charge storage characteristics is higher as the separator (separator body) is thinner.
  • one of the physical properties of the separator is the pore volume (film
  • the separator needs to be strong enough to withstand the process of manufacturing the battery in addition to ensuring insulation inside the battery.
  • the separator film thickness is reduced, the energy density of the battery is improved, but the film strength (tensile strength and piercing strength) is reduced, so the average pore diameter of the microporous material has to be reduced. The rate decreases.
  • the thickness of the Ceno router is large, the strength of the membrane can be secured to some extent, so that the average pore diameter and porosity of the microporous can be selected relatively freely.
  • the separator on which the coating layer can be installed has (I) a film thickness that can secure an energy density.
  • the pore volume of the separator body to which the present invention can be applied is 1500 (unit: ⁇ m.%) Or less calculated by film thickness X porosity.
  • the battery having a separator with a coating layer that is not related to the material of the separator body has a significant improvement in charge storage characteristics. If the thickness (X porosity) is 1500 (unit: m '%) or less, and especially 800 (unit: ⁇ m'%) or less, the effect can be exhibited remarkably.
  • the battery was designed so that the end-of-charge voltage was 4.20 V, and the positive / negative capacity ratio was designed to be 1.08 at this potential, in the same manner as in Example 1 of the first example. A battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery B1.
  • the battery was designed so that the end-of-charge voltage was 4.20V, and the capacity ratio of positive and negative electrodes was designed to be 1.08 at this potential, as in Example 2 of the first example. A battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery B2.
  • the battery was designed so that the end-of-charge voltage was 4.30 V, and the capacity ratio between the positive and negative electrodes was designed to be 1.08 at this potential, as in Example 1 of the first example.
  • a battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery B3.
  • the battery was designed so that the end-of-charge voltage was 4.30 V, and the capacity ratio of positive and negative electrodes was designed to be 1.08 at this potential, in the same manner as in Example 2 of the first example. A battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery B4.
  • the battery was designed so that the end-of-charge voltage was 4.35V, and the capacity ratio of positive and negative electrodes was designed to be 1.08 at this potential. A battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery B5.
  • the battery was designed so that the end-of-charge voltage was 4.35 V, and the capacity ratio of positive and negative electrodes was designed to be 1.08 at this potential, as in Example 2 of the first example. A battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery B6.
  • Batteries were produced in the same manner as in Examples 1 to 6 except that no coating layer was formed on the separator.
  • the batteries thus fabricated are hereinafter referred to as comparative batteries Y1 to Y6, respectively.
  • Tables 8 and 9 show the results of charging and storage characteristics (remaining capacity after storage) of the batteries ⁇ 1 to ⁇ 6 of the present invention and comparative batteries Y1 to ⁇ 6.
  • the table also shows the results of the batteries of the present invention Al, ⁇ 2 and the comparative batteries Zl, ⁇ 2.
  • charging / discharging conditions and storage conditions are as follows.
  • the present invention batteries Al, A2, B3 to B6 and the comparative batteries Zl, Z2, and Y3 to Y6 have the same conditions as the experiment of the first embodiment, and the present invention batteries Bl, ⁇ 2 and comparative batteries Yl, ⁇ 2
  • the condition is that it is left at 80 ° C for 4 days.
  • the present invention in which a cover layer was formed on the surface of the separator body despite the same separator (the separator body in the case of the battery of the present invention) was the same. It can be seen that the battery has a significantly improved remaining capacity after charging and storage compared to a comparative battery in which no coating layer is formed (for example, when comparing the present invention battery B1 with the comparative battery Y1, Inventive battery B2 and comparative battery Y2).
  • the degree of deterioration of the charge storage characteristics tends to be very large.
  • the batteries of the present invention (4), (6), and (2), in which the separator of these batteries is provided with a coating layer suppresses deterioration of the charge storage characteristics.
  • this effect is particularly effective when the pore volume of the separator (separator body) is 800 m '% or less, and the charge storage voltage is 4.30 V or more (lithium).
  • the positive electrode potential with respect to the reference electrode potential is 4.40V or more
  • the positive electrode potential with respect to the lithium reference electrode potential is 4.45V or more
  • the discharge operating voltage is improved, the remaining. This is effective in eliminating the charging behavior.
  • the end-of-charge voltage is 4.40V
  • the packing density of the positive electrode active material layer is 3.60gZcc
  • the separator (the separator body in the case of the battery of the present invention) is fixed to CS1, while the separator body
  • the solid content of titanium oxide with respect to acetone is 10% by mass and the concentration of water-insoluble binder with respect to titanium dioxide is 2% by mass.
  • a battery was fabricated in the same manner as in Example 1 of the first example except that the thickness was 1 ⁇ m.
  • the battery thus produced is hereinafter referred to as the present invention battery C1.
  • the solid content concentration of titanium oxide with respect to acetone is 10% by mass and the concentration of the water-insoluble binder with respect to titanium oxide is 30% by mass.
  • a battery was fabricated in the same manner as in Example 1 of the first example except that m was set.
  • the battery thus produced is hereinafter referred to as the present invention battery C2.
  • Table 10 shows the results of investigating the charge storage characteristics (remaining capacity after charge storage) of the batteries Cl and C2 of the present invention. The table also shows the results of the battery A1 of the present invention and the comparative battery Z1.
  • the charge / discharge conditions, the storage conditions, and the remaining capacity calculation method are the same as in the experiment of the first embodiment.
  • the filter function increases as the thickness of the coating layer increases and the concentration of the water-insoluble binder increases.
  • This is considered to be a trade-off relationship between the distance and the lithium ion permeability, and although not shown in Table 10, the concentration of the water-insoluble binder for titanium oxide is
  • the battery can only be charged / discharged about half of the design capacity, and it has been found that the function as a battery is greatly reduced. This is presumably because the water-insoluble binder was filled between the particles of the coating layer, and the lithium ion permeability was extremely lowered.
  • the amount of the water-insoluble binder is large, it is recognized that the air permeability is greatly reduced even before the electrolyte solution is absorbed and swollen.
  • the amount of the water-insoluble binder it is 0 times or less, preferably 1.5 times or less, particularly preferably 1.2 times or less. Even if the amount of the water-insoluble binder is 1% by mass, the water-insoluble binder is fairly uniformly dispersed in the coating layer by the dispersion treatment method such as the aforementioned Filmics method. In addition to adhesive strength, the filter function is very high.
  • the amount of water-insoluble binder is preferably as low as possible V, but considering the physical strength that can withstand the processing during battery fabrication, the effect of the filter, ensuring the dispersibility of inorganic particles in the slurry, etc. It is preferable to limit the amount to 1 to 50% by mass, preferably 1 to: LO mass%, particularly preferably 2 to 5% by mass, based on the filler particles.
  • the thickness of the coating layer it is preferable to limit the thickness of the coating layer to 2 m or less on one side (4 m or less on both sides) in order to suppress the deterioration of load characteristics and energy density of the battery. In particular, it is desirable to regulate to 1 ⁇ m or less on one side (2 ⁇ m or less on both sides).
  • the end-of-charge voltage is 4.40 V
  • the coating layer thickness is 2 ⁇ m
  • the separator is IS4 for the battery of the present invention
  • CS2 is for the comparative battery
  • the positive electrode active material layer is changed in packing density. The relationship between the packing density and the charge storage characteristics was investigated, and the results are shown below.
  • a battery was fabricated in the same manner as in Example 2 of the first example except that the packing density of the positive electrode active material layer was 3.20 gZcc.
  • the battery thus produced is hereinafter referred to as the present invention battery D1.
  • a battery was fabricated in the same manner as in Example 2 of the first example except that the packing density of the positive electrode active material layer was changed to 3.40 gZcc.
  • the battery thus produced is hereinafter referred to as the present invention battery D2.
  • a battery was fabricated in the same manner as in Comparative Example 2 of the first example except that the packing density of the positive electrode active material layer was 3.20 g / cc.
  • the battery thus produced is hereinafter referred to as comparative battery XI.
  • a battery was fabricated in the same manner as in Comparative Example 2 of the first example except that the packing density of the positive electrode active material layer was 3.40 g / cc.
  • the battery thus produced is hereinafter referred to as comparative battery X2.
  • a battery was fabricated in the same manner as in Comparative Example 2 of the first example except that the packing density of the positive electrode active material layer was 3.80 g / cc.
  • the battery thus produced is hereinafter referred to as comparative battery X3.
  • Table 11 shows the results of the charge storage characteristics (remaining capacity after charge storage) of the batteries D1 and D2 of the present invention and the comparative batteries X1 to X3.
  • the present invention The results for pond A2 and comparative battery Z2 are also shown.
  • the charge / discharge conditions, the storage conditions, and the remaining capacity calculation method are the same as in the experiment of the first embodiment.
  • the deterioration in the outermost layer is the center, and in comparative batteries Z2, X2, and X3, the penetration / diffusion of lithium ions into the positive electrode active material during discharge becomes rate-limiting and deteriorates.
  • the batteries A2 and D2 of the present invention since the deterioration of the outermost surface layer is suppressed due to the presence of the coating layer, the penetration and diffusion of lithium ions into the positive electrode active material during discharge is rate-limiting. Therefore, it is estimated that the degree of deterioration is reduced.
  • the packing density of the positive electrode active material layer is 3.40 gZcc or more.
  • the packing density of the negative electrode active material layer and the type of active material are not particularly limited.
  • End-of-charge voltage is 4.40V
  • packing density of positive electrode active material layer is 3.60gZcc
  • separator book While fixing the physical properties of the coating layer formed on the surface of the body (the concentration of titanium oxide, polymer concentration, CMC concentration, surfactant concentration, and coating layer thickness with respect to the total amount of slurry), the separator (the present invention In the case of batteries, the separator body was changed, and the relationship between the physical properties of the separator and the charge storage characteristics was examined. The results are shown below.
  • Example 1 the battery shown in the second mode in the best mode was used.
  • the battery thus produced is hereinafter referred to as the present invention battery E1.
  • a battery was fabricated in the same manner as in Example 1, except that a separator having an average pore diameter of 0.1 m, a film thickness of 12 ⁇ m, and a porosity of 38% was used. Since the thickness of the coating layer is, the total thickness of the separator is 14 ⁇ m.
  • the battery thus produced is hereinafter referred to as the present invention battery E2.
  • a battery was fabricated in the same manner as in Example 1 except that a separator having an average pore diameter of 0.6 m, a film thickness of 23 ⁇ m, and a porosity of 48% was used. Since the thickness of the coating layer is, the total thickness of the separator is 25 ⁇ m.
  • the battery thus produced is hereinafter referred to as the present invention battery E3.
  • a battery was fabricated in the same manner as in Example 1 except that the separator coating layer was disposed on the positive electrode side.
  • comparative battery W1 The battery thus produced is hereinafter referred to as comparative battery W1.
  • a battery was fabricated in the same manner as in Example 2 except that the separator coating layer was disposed on the positive electrode side.
  • comparative battery W2 The battery thus produced is hereinafter referred to as comparative battery W2.
  • the charge storage characteristics (remaining capacity after charge storage) of the present invention batteries E1 to E3 and the comparative batteries Wl and W2 were examined, and the results are shown in Table 12.
  • the table shows the comparative battery.
  • the results of Zl to comparative battery Z6 are also shown. Also, based on the results obtained here, the correlation between the physical properties of the separator (separator body) and the remaining capacity after storage after charging was examined. The results are shown in Fig. 5.
  • the charge / discharge conditions and the storage conditions are the same as those in the experiment of the first embodiment.
  • Copolymer refers to a copolymer containing an attarilonitrile structure (unit).
  • the coating voltage was 4.40 V and the packing density of the positive electrode active material layer was 3.60 g / cc. It can be seen that the formed batteries E1 to E3 of the present invention have a significantly improved remaining capacity compared to the comparative batteries Z1 to Z6 in which the coating layer is not formed.
  • the reason for this experimental result is that, as shown in the experiment of the first embodiment, the electrolytic solution decomposed on the positive electrode and Co eluted from the positive electrode are trapped in the coating layer, so that the separator body It is presumed that the deposition ⁇ reaction (deterioration) and clogging due to movement to the negative electrode are suppressed, that is, the coating layer functions as a filter.
  • the water-insoluble binder used this time has been confirmed to be electrochemically stable due to its CV characteristics, when water is generally used as a solvent, it tends to be weak against acid.
  • the above binders, thickeners, and surfactants are often required, but as for the cause of oxidation (decomposition), which of the three substances is strong. Whether it is affected is unknown at this time, and it is highly possible that the effect is due to the combination.
  • the specific decomposition potential is unknown, but as long as various materials and conditions are used, the temperature is about 50 ° C, and in the case of potential, the positive potential is 4 at the Li reference potential. It became clear that this tendency became stronger when the voltage became 40V or more.
  • the stability due to the cycle characteristics at 45 ° C and 60 ° C showed the same tendency as the force evaluated.
  • a battery using a separator with a coating layer on the negative electrode side shows performance equal to or better than a battery using a separator without a coating layer, but a battery using a separator with a coating layer on the positive electrode side.
  • gas generation and capacity deterioration due to decomposition were observed in several cycles.
  • a coating layer is formed on the positive electrode side Normal battery performance evaluation (
  • the power for improving the charge storage characteristics is higher as the separator (separator body) is thinner.
  • the pore volume (film thickness X porosity) which is one of the physical properties of the separator and greatly affects the film thickness, is used as an index, as shown in Fig. 5, approximately 1500 (unit: zm '% )
  • the effect of the present invention was sufficiently exhibited, and it was particularly noticeable that the effect of the present invention appeared remarkably at about 800 (unit: / zm ′%). This is considered to be due to the same reason as shown in the experiment of the first embodiment.
  • the pore volume (film thickness X porosity) of the separator body is preferably 1500 (unit: ⁇ m-%) or less, particularly 800 (unit: / zm '%) or less. .
  • separator body in the case of the battery of the present invention
  • packing density of the positive electrode active material layer was 3.60 gZcc
  • physical properties of the coating layer formed on the surface of the separator body titanium oxide relative to the total amount of slurry
  • Copolymer containing acrylonitrile structure (unit) Copolymer containing acrylonitrile structure (unit), CMC, and surfactant concentration and coating layer thickness
  • the battery was designed so that the end-of-charge voltage was 4.20 V, and the capacity ratio of positive and negative electrodes was designed to be 1.08 at this potential, in the same manner as in Example 1 of the fifth example. A battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery F1.
  • the battery thus produced is hereinafter referred to as the present invention battery F2.
  • the battery was designed so that the end-of-charge voltage was 4.30 V, and the capacity ratio between the positive and negative electrodes was designed to be 1.08 at this potential. A battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery F3.
  • the battery was designed so that the end-of-charge voltage was 4.30 V, and the capacity ratio of positive and negative electrodes was designed to be 1.08 at this potential, as in Example 2 of the fifth example. A battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery F4.
  • the battery was designed so that the end-of-charge voltage was 4.35V, and the capacity ratio of positive and negative electrodes was designed to be 1.08 at this potential, as in Example 2 of the fifth example. A battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery F5.
  • a battery was fabricated in the same manner as in Example 2 except that the separator coating layer was disposed on the positive electrode side.
  • comparative battery VI The battery thus produced is hereinafter referred to as comparative battery VI.
  • a battery was fabricated in the same manner as in Example 4 except that the separator coating layer was disposed on the positive electrode side.
  • comparative battery V2 The battery thus produced is hereinafter referred to as comparative battery V2.
  • Example 5 Battery as in Example 5 except that the separator coating layer was disposed on the positive electrode side. Was made.
  • comparative battery V3 The battery thus produced is hereinafter referred to as comparative battery V3.
  • ⁇ Copolymer refers to a copolymer containing an acrylonitrile structure (unit).
  • the separator (the separator body in the case of the present invention batteries F1 to F5, El and E2 and comparative batteries V1 to V3, Wl and W2) is the same. Regardless, the batteries F1 to F5, El, and E2 of the present invention in which the coating layer is formed on the negative electrode side of the separator body are compared with the comparative batteries Y1 to Y6, Zl, and ⁇ 2 that are not formed with the coating layer. It is observed that the remaining capacity is greatly improved (for example, when the present invention battery F1 is compared with the comparative battery Y1, or when the present invention battery F2 is compared with the comparative battery ⁇ 2).
  • the degree of deterioration of the charge storage characteristics tends to be very large.
  • the batteries F4, F5 and E2 of the present invention in which the coating layer was provided on the negative electrode side of the separator body of these batteries, it was recognized that the deterioration of the charge storage characteristics was suppressed.
  • the batteries F2, F4, F5, El, and E2 of the present invention in which the coating layer was formed on the negative electrode side of the separator body were coated on the positive electrode side of the separator body. It is observed that the remaining capacity after charge storage is significantly improved compared to the comparative batteries V1 to V3, Wl, and W2 in which the layers are formed (for example, when the present invention battery F2 is compared with the comparative battery VI) Or when the present invention battery F4 and the comparative battery V2 are compared).
  • this effect is particularly effective when the pore volume of the separator (separator body) is 800 m '% or less, and the charge storage voltage is 4.30 V or more (lithium).
  • the positive electrode potential with respect to the reference electrode potential is 4.40V or more
  • the positive electrode potential with respect to the lithium reference electrode potential is 4.45V or more
  • the end-of-charge voltage is 4.40 V
  • the packing density of the positive electrode active material layer is 3.60 gZcc
  • the separator (the separator body in the case of the battery of the present invention) is fixed to CS1
  • the coating layer formed on the surface of the separator body The physical properties (concentration of copolymer containing acrylonitrile structure with respect to the total amount of slurry) were changed, and the relationship between the physical properties of the coating layer and the charge storage characteristics was examined. The results are shown below.
  • the slurry used for forming the separator coating layer was the same as Example 1 of the fifth example except that the concentration of the copolymer containing the atta-tolyl structure relative to the total amount of the slurry was 0.5% by mass. Thus, a battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery G1.
  • the slurry used for forming the coating layer of the separator was the same as that of Example 1 of the fifth example except that the concentration of the copolymer containing the atta-tolyl structure relative to the total amount of the slurry was 2% by mass. A battery was produced.
  • the battery thus produced is hereinafter referred to as the present invention battery G2.
  • the slurry used when forming the coating layer of the separator was the same as that described above except that the concentration of the copolymer containing the atta-tolyl structure relative to the total amount of the slurry was 5% by mass and the thickness of the coating layer was 3 m. Batteries were produced in the same manner as in Example 1 of 5 examples.
  • the battery thus produced is hereinafter referred to as the present invention battery G3.
  • Table 15 shows the results of the charge storage characteristics (remaining capacity after charge storage) of the batteries G1 to G3 of the present invention. The table also shows the results of the battery E1 of the present invention and the comparative battery Z1.
  • the charge / discharge conditions, the storage conditions, and the remaining capacity calculation method are the same as in the experiment of the first embodiment.
  • Copolymer refers to a copolymer containing an acrylonitrile structure (unit).
  • the batteries El and G1 to G3 of the present invention in which the covering layer was formed on the negative electrode side of the separator main body were compared with the comparative battery Z1 in which the covering layer was not formed. It can be seen that the remaining capacity after charge storage is greatly improved.
  • the present invention batteries El and G1 to G3 are compared, the remaining capacity after charge storage depends on the concentration of the copolymer (non-water-soluble binder) containing the acrylonitrile structure relative to the total amount of the slurry and the thickness of the coating layer. It was found that it was hardly affected.
  • the concentration of the copolymer (non-water soluble binder) containing the acrylonitrile structure relative to the total amount of solids (total amount of titanium oxide, copolymer containing the acrylonitrile structure, CMC, and surfactant) is 10% by mass. It is preferably 5% by mass or less, particularly preferably 3% by mass or less.
  • the thickness of the coating layer is preferably regulated to 4 m or less in order to suppress a decrease in load characteristics and a decrease in energy density of the battery. It has been confirmed that the effect of the present invention is exhibited when the thickness of the coating layer is about L m.
  • the end-of-charge voltage is 4.40 V
  • the coating layer thickness is 2 ⁇ m
  • the separator is IS15 for the battery of the present invention
  • CS2 is for the comparative battery.
  • the relationship between the packing density and the charge storage characteristics was investigated, and the results are shown below.
  • a battery was fabricated in the same manner as in Example 2 of Example 5 except that the packing density of the positive electrode active material layer was 3.20 gZcc.
  • the battery thus produced is hereinafter referred to as the present invention battery HI.
  • a battery was produced in the same manner as described above.
  • the battery thus produced is hereinafter referred to as the present invention battery H2.
  • the charge storage characteristics (remaining capacity after charge storage) of the inventive batteries Hl and H2 were examined. The results are shown in Table 16. The table also shows the results of the battery E2 of the present invention and the comparative batteries Z2, X1 to X3, and W2.
  • the charge / discharge conditions, the storage conditions, and the remaining capacity calculation method are the same as in the experiment of the first embodiment.
  • 'Comparative batteries XI to X 3 and Z 2 do not have a coating layer, so only the separator body constitutes the separator.
  • 'Copolymer' refers to a copolymer containing an acrylonitrile structure (unit).
  • the packing density of the positive electrode active material layer is 3.40 gZcc or more.
  • the packing density of the negative electrode active material layer and the type of active material are not particularly limited.
  • the end-of-charge voltage was 4.40V
  • the separator was IS 17 for the battery of the present invention
  • CS2 was used for the comparative battery.
  • the battery shown in the third mode in the best mode was used.
  • the battery thus produced is hereinafter referred to as the present invention.
  • a battery was fabricated in the same manner as in the above example except that LiBF was not added to the electrolytic solution.
  • comparative battery VI The battery thus produced is hereinafter referred to as comparative battery VI.
  • a battery was prepared in the same manner as in the above example except that the coating layer was not formed on the surface of the separator body.
  • comparative battery V2 The battery thus produced is hereinafter referred to as comparative battery V2.
  • comparative battery V3 The battery thus produced is hereinafter referred to as comparative battery V3.
  • the charge storage characteristics (remaining capacity after charge storage) of the present invention [and comparative batteries V1 to V3 were examined, and the results are shown in Table 17.
  • Charge / discharge conditions and storage conditions are as follows.
  • the charging / discharging interval is 10 minutes.
  • the charging / discharging is performed once under the above charging / discharging conditions, and the battery charged to the set voltage under the above charging conditions is left again at 60 ° C for 5 days.
  • the battery is cooled to room temperature, discharged under the same discharge conditions as described above, and the remaining capacity is measured.
  • the remaining capacity was calculated from the equation.
  • the coating layer is formed on the surface of the separator body.
  • Comparative battery V2 that does not form a coating layer on the surface of the main body, and LiBF is not added to the electrolyte
  • a coating layer is formed on the positive electrode surface of the separator body!
  • Invention has a remaining capacity compared to Comparative Battery VI, which does not contain LiBF in the electrolyte.
  • the LiBF-derived film becomes the positive electrode active material.
  • the comparative battery VI in which the separator layer is formed on the separator body has a coating layer formed on the separator body, so that the remaining capacity is larger than that of the comparative battery V3. Is recognized.
  • a battery in which LiBF is added to the electrolyte the present invention 3 ⁇ 4J, comparative battery
  • the battery J of the present invention in which the separator layer is formed on the separator body has a larger remaining capacity than the comparative battery V2 in which the separator layer is not formed on the separator body. Is recognized. This is considered to be due to the following reasons.
  • LiBF is added to the electrolyte solution as described above, the LiBF-derived film becomes a surface of the positive electrode active material.
  • the coating layer is formed on the separator body as described above, the electrolytic solution component decomposed on the positive electrode and the Co ion isotropic force coating layer that also eluted the positive electrode force are trapped, and the separator moves to the negative electrode. Deposition ⁇ reaction (deterioration) and clogging are suppressed, that is, the coating layer exhibits a filter function, and Co and the like are suppressed from being deposited on the negative electrode. As a result, it is considered that the battery with the coating layer is improved in charge storage performance as compared with a battery having a coating layer.
  • the binder of the coating layer does not inhibit the air permeability at the time of producing the separator, but many of the binders swell about twice or more after the injection of the electrolytic solution. The space between the particles is filled.
  • This coating layer is complicated and the inorganic particles are firmly adhered to each other by the noinder component, so that the strength is improved and the filter effect is sufficiently exerted (intricate even if the thickness is small). (It is a structure and the trapping effect is enhanced).
  • the filter effect depends on the thickness of the polymer layer, so the thickness of the polymer layer is increased. Otherwise, the effect will not be fully exerted, and the force will also swell the polymer.
  • the function of the filter is reduced if the structure is not completely porous and non-porous.
  • the negative effect such as the deterioration of the permeability of the electrolyte solution to the negative electrode and the deterioration of the load characteristics increases. Therefore, in order to minimize the influence on other properties while exerting the filter effect, it is more preferable to use inorganic particles (in this example, acid It is advantageous to form a coating layer (one filter layer) comprising
  • the positive electrode active material is formed by adding LiBF to the electrolyte.
  • the film formed on the positive electrode surface becomes thicker.
  • the film thicknesses on the positive electrode surface and the negative electrode surface are determined by appropriately defining the lithium salt concentration and the amount of LiBF added.
  • the concentration of LiPF in the electrolyte was 0.6M or more and 2.0M or less.
  • the ratio of LiBF to the total amount of non-aqueous electrolyte is 0.1 mass% or more 5.0 mass It was found that it is preferable to regulate to less than%. As a result, LiBF
  • LiBF is highly reactive with the positive electrode, the lithium salt concentration is reduced and the electrolyte conductivity is reduced.
  • the reaction product moves to the negative electrode of the separator and deposits ⁇ reacts (deteriorates), or the separator is clogged. In this way, the charge storage characteristics can be greatly improved.
  • a separator body with an average pore diameter of 0.1 m, a film thickness of 16 ⁇ m, and a porosity of 47%, and a coating layer is provided on the negative electrode side surface of the separator body, and the ratio to the total mass of the electrolyte A battery was fabricated in the same manner as in the ninth example except that the content was changed to 3% by mass.
  • the battery thus produced is hereinafter referred to as the present invention battery K.
  • a battery was prepared in the same manner as in the above example except that the coating layer was not formed on the surface of the separator body.
  • comparative battery U1 The battery thus produced is hereinafter referred to as comparative battery U1.
  • a battery was fabricated in the same manner as in the above example except for the above.
  • comparative battery U2 The battery thus produced is hereinafter referred to as comparative battery U2.
  • Table 18 shows the results of charging and storage characteristics (remaining capacity after storage) of the present invention battery K and comparative batteries Ul and U2.
  • the charge / discharge conditions, storage conditions, and remaining capacity calculation method are the same as those in the experiment of the ninth example.
  • the battery K of the present invention in which a coating layer was formed on the negative electrode side surface of the separator body and LiBF was added to the electrolyte,
  • the remaining capacity is larger than that of the comparative battery U2 (the charge storage characteristics are improved) when a coating layer is formed on the surface of the main body of the palator.
  • the coating layer is formed on the surface of the separator body. This is thought to be due to the fact that the filter effect is exerted by forming the film. Therefore, it can be seen that a coating layer may be formed on the negative electrode side surface of the separator body.
  • the battery characteristics are improved when the coating layer is formed on the positive electrode side surface of the separator main body than when the coating layer is formed on the negative electrode side surface of the separator body (comparative battery).
  • the characteristics of the battery of the present invention with respect to the comparative battery V2 shown in the ninth example are larger than the characteristics of the battery of the present invention K with respect to U1). Therefore, it is preferable to form a coating layer on the positive electrode side surface of the separator body.
  • the material of the water-insoluble binder is not limited to a copolymer containing acrylonitrile units.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • SBR styrene butadiene rubber
  • the coating layer is not limited to being formed on both sides of the separator body, but may be formed only on one side.
  • the material of the water-insoluble binder is not limited to a copolymer containing an acrylonitrile unit, but other acrylic polymers, nitrile polymers, gen polymers, copolymers thereof, and the like.
  • Non-fluorine containing polymers are desirable.
  • Fluorine-containing polymers such as PVDF and PTFE can also be used, but in order to fully demonstrate the function of being able to exert binding power with a small amount of addition and being flexible, it is necessary to use a non-fluorine-containing polymer. In particular, it is preferable to use an acrylic polymer.
  • the amount of the water-insoluble polymer added is the total amount of solids (particles forming the porous layer, and in the above examples, the filler particles, the water-insoluble binder, the water-soluble binder, and the surfactant) 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less. Further, it is desirable that the content is 0.5% by mass or more in order to fully exhibit the binding property. Further, since the coating layer is disposed on the negative electrode side of the separator body, it does not come into direct contact with the positive electrode, and the stability with respect to the positive electrode potential does not require special consideration. However, it is preferable to use a material that is known in advance to decompose at the positive electrode potential, such as SBR that is electrochemically unstable at about IV.
  • water-soluble polymers include cellulosic polymers such as CMC, and their ammonium salts, alkali metal salts, polyacrylic acid ammonium salts, and polycarboxylic acid ammonia. And salt.
  • the added amount of these water-soluble polymers is preferably 10% by mass or less, preferably 0.5% by mass or more and 3% by mass or less, based on the total amount of solids.
  • the type of surfactant is not particularly limited, but a nonionic surfactant is preferable in consideration of the influence on the battery performance inside the lithium ion battery. Also these interfaces
  • the addition amount of the activator is 3% by mass or less, preferably 0.5% by mass or more and 1% by mass or less, based on the total amount of solids.
  • the total amount of solids excluding filler particles relative to the total amount of solids may be 30% by mass or less. desirable.
  • the positive electrode active material is not limited to the above-mentioned lithium cobaltate, but includes cobalt-nickel-manganese lithium composite oxide, aluminum nickel manganese lithium composite oxide, aluminum nickel cobalt composite oxide, etc.
  • lithium composite oxide containing cobalt or manganese, spinel type lithium manganate, etc. may be used.
  • it is a positive electrode active material whose capacity is increased by further charging with respect to a specific capacity of 4.3 V at a lithium reference electrode potential, and preferably has a layered structure.
  • these positive electrode active materials can be used alone or mixed with other positive electrode active materials!
  • the method of mixing the positive electrode mixture is not limited to the wet mixing method, and is a method in which the positive electrode active material and the conductive agent are dry mixed in advance, and then PVDF and NMP are mixed and stirred. It may be.
  • the negative electrode active material is not limited to the above-mentioned graphite, but can insert and desorb lithium ions, such as graphite, coatas, tin oxide, metallic lithium, silicon, and mixtures thereof. If so, what type is it?
  • Lithium salt of electrolyte in the case of the third form, lithium salt mixed with LiBF
  • LiN (SO CF), LiN (SO C F), Li
  • the concentration of the lithium salt is not particularly limited, but it is desirable to regulate it to 0.8 to 1.5 mol per liter of the electrolyte.
  • the solvent of the electrolyte solution is not limited to ethylene carbonate (EC) or jetyl carbonate (DEC), but propylene carbonate (PC), y butyrolatatane (GBL), ethyl methyl carbonate (EMC) Carbonate solvents such as dimethyl carbonate (DMC) are more preferred. A combination of cyclic carbonate and chain carbonate is desirable.
  • the present invention is not limited to a liquid battery, but can be applied to a gel polymer battery.
  • the polymer material in this case include polyether solid polymer, polycarbonate solid polymer, polyacrylonitrile solid polymer, oxetane polymer, epoxy polymer, and a copolymer of two or more of these, Cross-linked polymers or PVDF are exemplified, and a solid electrolyte formed by combining this polymer material, a lithium salt and an electrolyte into a gel can be used.
  • the present invention can be applied to, for example, a drive power source of a mobile information terminal such as a mobile phone, a notebook personal computer, and a PDA, and in particular, a use requiring a high capacity. It can also be expected to be used in high output applications that require continuous driving at high temperatures and in applications where the battery operating environment is severe, such as HEVs and power tools.
  • FIG. 1 is a graph showing the relationship between the change in the crystal structure of lithium cobaltate and the potential.
  • FIG. 2 is a graph showing the relationship between the remaining capacity after charge storage and the pore volume of the separator.
  • FIG. 3 is a graph showing the relationship between charge / discharge capacity and battery voltage in comparative battery Z2.
  • FIG. 4 is a graph showing the relationship between charge / discharge capacity and battery voltage in the battery of the present invention A2.
  • FIG. 5 is a graph showing the relationship between the remaining capacity after charge storage and the pore volume of the separator. Explanation of symbols

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Abstract

L'invention concerne une batterie électrolytique non aqueuse qui est excellente en matière de caractéristiques cycliques et de caractéristiques de stockage à températures élevées et est très fiable même si elle est construite avec une capacité élevée. L'invention concerne également un procédé de fabrication d'une batterie électrolytique non aqueuse de ce type. L'invention concerne en particulier une batterie électrolytique non aqueuse qui est caractérisée en ce que le matériau actif à électrode positive contient au moins du cobalt ou du manganèse, en ce qu'un séparateur est composé d'un corps principal de séparateur poreux et d'une couche de revêtement formée sur au moins une surface du corps principal du séparateur, et en ce que la couche de revêtement contient des particules de remplissage et un liant.
PCT/JP2007/055446 2006-03-17 2007-03-16 Batterie électrolytique non aqueuse et son procédé de fabrication WO2007108426A1 (fr)

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JP2006171450A JP4958484B2 (ja) 2006-03-17 2006-06-21 非水電解質電池及びその製造方法
JP2006207450A JP5110817B2 (ja) 2006-03-17 2006-07-31 非水電解質電池
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Cited By (8)

* Cited by examiner, † Cited by third party
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WO2010074202A1 (fr) * 2008-12-26 2010-07-01 日本ゼオン株式会社 Separateur pour batterie secondaire au lithium-ion et batterie secondaire au lithium-ion associee
CN101807714A (zh) * 2009-02-16 2010-08-18 三洋电机株式会社 非水电解质二次电池及其制造方法
EP2282364A1 (fr) * 2008-03-31 2011-02-09 Zeon Corporation Film poreux et électrode de pile rechargeable
WO2011108119A1 (fr) * 2010-03-05 2011-09-09 トヨタ自動車株式会社 Batterie secondaire au lithium et séparateur à utiliser dans ladite batterie
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JP2015026609A (ja) * 2013-06-21 2015-02-05 住友化学株式会社 積層多孔質フィルム、非水電解液二次電池用セパレータ及び非水電解液二次電池
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